煤直接液化油中混合酚的分离研究

利用分子筛择形特点，对煤直接液化油中的混合酚实施高效分离。本研究选取间甲酚和对甲酚作为分离煤直接液化油馏分段混合酚的模型化合物，采用化学液相沉积法对HZSM-5吸附剂的孔口结构进行改变，分析分子筛硅铝比及颗粒粒径对模型化合物间甲酚和对甲酚吸附分离性能的影响，以获得高性能固相吸附剂，并将其应用于180-190℃馏分段混合酚分离。结果表明，当分子筛硅铝比为25、粒径为3-5 μm时，分子筛的孔口结构调节效果最优；当正硅酸乙酯的最小用量为0.2 mL/g时，固相吸附剂的吸附量为0.03 g/g，对甲酚选择性高于95%。由于外表面沉积物对吸附剂的孔口结构变化，导致对甲酚选择性的提高。进一步采用HZSM-5（1）吸附剂对真实煤直接液化油混合酚的分离中发现，苯酚和对甲酚的选择性均达到100%。     

燃煤烟气中As、Se、Pb的形态分布及S、Cl元素对其形态分布的影响

基于化学热力学平衡分析方法，计算分析了燃煤烟气中重金属As、Se、Pb的形态分布规律，研究了S、Cl等元素对As、Se、Pb的形态分布规律的影响。结果表明，氧化性气氛下，As以As₂O₅、As₄O₆、AsO等氧化物的形式存在；Se主要以SeO₂形式存在；Pb在1000 K以下主要是固态PbSO₄，1200 K以上为气态PbO。还原性气氛下，As在较低温度时为固态As₂S₂，900-1400 K以As₂、AsS、AsN气体共存，2000 K以上全部转化为气态AsO。Se在1100 K以下主要以气态H₂Se存在，1100 K开始生成SeS和Se₂气体，1800 K时主要是气态Se和少量气态SeO；Pb在中低温时主要是PbS，1800 K以上气态Pb为主要存在形态。S在还原性气氛下增大了AsS（g）、PbS（g）、SeS（g）的比例，氧化性气氛下对As、Se、Pb形态分布基本无影响；Cl无论在氧化还是还原气氛下对As、Se影响均较小，但对Pb的形态分布影响较大。     

Study on fluorescence property of dopamine and determination of dopamine by fluorimetry

In this study, a rapid and sensitive high performance liquid chromatography-inductively coupled plasma-mass spectrometry (HPLC-ICP-MS) determination of primary As species in fish tissues and urine is reported. The separation was achieved on an Altima C18 column with a mobile phase containing citric acid and hexanesulfonic acid (pH 4.5). As(V), monomethylarsonic acid (MMA), As(III), dimethylarsinic acid (DMA) and arsenobetaine (AsB) were separated in less than 4 min with retention times of 83, 99, 130, 166 and 208 s, respectively. This separation of five species in less than 4 min should be attractive to those interested in As speciation. The quantification limits were 44, 56, 94, 64, 66 ng l(-1) and the relative standard deviations (R.S.D.) for day-to-day injections of As at 2 mug l(-1) were 2.0, 3.1, 2.4, 3.8 and 4.0%. The procedure was tested using two reference materials (DORM-2 dogfish muscle tissue, NIST SRM 2670 Freeze-dried Urine, normal level) and then applied to real-world samples. The results obtained demonstrate the suitability of the procedure for screening and quantification at physiological levels of primary As species in biological samples.     

Important role of the 3-mercaptopropionamide moiety in glutathione: promoting effect on decomposition of the adduct of glutathione with the oxoammonium ion of TEMPO

Cyclic voltammetry of TEMPO in aqueous 0.1 M NaOH in the presence of glutathione (GSH) or cysteine (Cys) indicated the following points: (i) Both of the thiols rapidly formed adducts 3 with oxoammonium ion 1 anodically generated from TEMPO. (ii) 3 generated from GSH entered a succeeding reaction that generated N-oxide anion 2- (the reduced TEMPO). (iii) 3 produced from Cys remained intact over the time scale of voltammetry. A structural feature of GSH was considered to contribute to the observed behavior of this tripeptide. Possible structural features were evaluated by screening various thiols on the basis of whether they provided GSH-like voltammetric results. The 3-mercaptopropionamide group with an amide hydrogen in GSH was determined to be responsible for the observed difference between GSH and Cys. The likely function is to transform 3 from GSH into a 5-imino-1,2-oxathiolane intermediate, thereby releasing 2-. Product analysis for reactions of model thiols representing GSH and Cys with 1 provided support for this argument and suggested that the reaction of GSH or Cys with 1 would produce the corresponding disulfides, regardless of whether a five-membered ring intermediate was formed. The proposed function of the 3-mercaptopropionamide moiety of GSH may provide useful insight for the molecular design of exogenous thiol compounds as novel drugs for the treatment of GSH-depletion-related disorders.     

La2Zr2O7催化剂结构相变对甲烷氧化偶联反应性能的影响

采用共沉淀法并通过改变焙烧温度制备了一系列具有不同晶相结构的La₂Zr₂O₇催化剂，在微型固定床反应器上评价其甲烷氧化偶联反应性能，并利用XRD、Raman、CO₂-TPD、XPS等表征手段，探究催化剂的物相结构、表面碱性以及表面氧物种的变化规律。结果表明，随着焙烧温度从700℃逐渐升高到1200℃，La₂Zr₂O₇催化剂结晶度不断提高，晶相发生明显变化，从无定形结构逐渐向缺陷萤石结构过渡，最终转变成烧绿石结构。焙烧温度提高促使La₂Zr₂O₇晶相转变过程中，催化剂表面的碱性强度减弱，中等碱性位数量以及具有催化活性的表面氧物种O₂^2-和O₂^-的相对含量不断减少，致使催化剂的CH₄转化率和C₂₊选择性不断降低。其中，无定形LZO-CP-700催化剂表现出最佳的甲烷氧化偶联反应性能。     

家禽肌肉组织中硝基咪唑类药物残留的液相色谱串联质谱测定

建立了同时检测家禽肌肉组织中3种硝基咪唑类药物残留的液相色谱-串联质谱法。样品用乙酸乙酯提取，经浓缩、过滤后直接进入液相色谱-质谱分析。采用监测母离子及其相应子离子的多反应监测技术，根据离子流峰面积进行定量。3种药物的定量检出限分别为甲硝唑0．8μg／kg、洛硝哒唑0．1μg／kg、二甲硝唑0．1μg／kg。1次分析的运行时间为5min。是一种快速、灵敏、可靠的分析方法。     

Moclobemide-selective membrane electrode and its pharmaceutical applications

A liquid membrane electrode prepared with moclobemide-dipicrylamine ion-pair complex, dissolved in nitrobenzene as solvent, was studied for analytical performance. The linear response covers the range 10(-3)-10(-6) M moclobemide solution, with a slope of 50.7 mV decade(-1) (pH range 3.5-8). The detection limit is 3 x 10(-7) M. The electrode shows stability, good reproducibility and fast response. The selectivity of the electrode is good. There are two important interfering ions: mianserin and thiamine (Vitamin B(1)). The compression excipients (such as Mg(2+), starch, talcum powder) do not interfere. These characteristics of the electrode enabled it to be used for the determination of moclobemide in drugs and as an active substance, via indirect and direct potentiometric methods. Via an indirect potentiometric method moclobemide, as an active substance, can be determined with an average recovery of 99.96% and a relative standard deviation of 0.85%, and this method can also be used for its determination in drugs with a relative standard deviation of < 2%. The electrode is useful for the determination of the dissolution rate of moclobemide tablets. The physical processes are numerically simulated by typical equations. The apparent first-order rate constants for disintegration and dissolution were calculated.